Porous PTFE materials and articles produced therefrom

ABSTRACT

Novel porous PTFE membranes are described possessing a unique combination of high strength, low flow resistance, and small pore size. Additionally, unique constructions with superior filtration and venting properties incorporating porous PTFE membranes are described.

RELATED APPLICATIONS

The present application is a continuation application of U.S. patentapplication Ser. No. 11/184,706, filed Jul. 18, 2005.

FIELD OF THE INVENTION

The present invention relates to porous PTFE membranes with acombination of high air or liquid permeability and small pore size andfilter materials made therefrom.

DEFINITIONS

As used in this application, the term “filtration efficiency” means thepercentage of particles within a specified size range captured by afiltration material, or media, at a given flow rate.

As used in this application, the term “flow” means the passage of afluid through a membrane or filter material. The term “flow rate” meansthe volume of flow per unit time and the term “flow resistance” meansthe restriction of flow as results during flow through membranes ormedia with small pores.

As used in this application, the term “permeability” means the abilityto transmit fluids (liquid or gas) through the pores of a membrane orfilter material when the material is subjected to a differentialpressure across it. Permeability can be characterized by Gurley number,Frazier number, or water flux rate.

As used in this application, the term “pore size” means the size of thepores in porous membranes. Pore size can be characterized by bubblepoint, mean flow pore size, or water entry pressure, as described inmore detail herein.

As used in this application, the term “water entry pressure” means thepressure required to drive water droplets through a membrane, as furtherdescribed in the test methods contained herein.

BACKGROUND OF THE INVENTION

Ideal filtration membranes possess adequate strength for the intendedapplications and combine high air or liquid permeability properties withhigh filtration efficiencies. High permeability or high flow through themembrane for a given pressure drop across the membrane affords lowerenergy costs due to lower energy loss and more rapid filtration times.Additionally, these features make it possible to install smaller, morecost effective systems. Improved filtration efficiency affords improvedcapture of contaminants. Typically, optimizing either filtrationefficiency or permeability comes at the expense of compromising theother. For example, in order to capture smaller particles, the membranemust possess small pores, but the smaller pore size typically increasesflow resistance and therefore decreases the liquid or gas permeabilitythrough the membrane. Similarly, increasing flow through the membrane isreadily achieved by increasing the pore size of the filter media, but indoing so the membrane captures fewer particles and is less efficient inthe capture of smaller particles.

Improvement in the development of filtration media has focused onfinding ideal combinations of high permeability, small pore size, andhigh strength. Expanded PTFE (ePTFE) membranes have enjoyed greatsuccess in the fields of liquid and gas filtration. Expanded PTFEmembranes are typically hydrophobic unless treated or modified orotherwise altered. Such membranes not only possess high chemicalinertness and thermal stability at extremes of temperature, but theyalso possess high strength.

Methods for processing expanded PTFE and articles made therefrom aretaught in U.S. Pat. No. 5,476,589 to Bacino. Bacino teaches very thinarticles consisting essentially of microfibrils. This patent enables theprocessing of high strength PTFE articles possessing small pore sizesand high air permeability not previously obtainable. The articles aremade by transversely stretching PTFE, then expanding it in thelongitudinal and transverse directions. These materials, albeit havingimproved filtration performance compared to predecessor membranes, havelimitations in their ability to satisfy increasingly demandingcommercial needs.

It is well established in the art that increasing the ratio of expansionof PTFE typically increases the pore size of resulting porous expandedarticles. The larger pore size results in lower flow resistance throughthe membranes, but, as noted above, at the expense of filtrationefficiencies, especially for smaller particles. Further stretching tendsto decrease membrane thickness which can result in a reduction in flowresistance.

Thus, while numerous efforts have been made to improve the filtrationcharacteristics of PTFE membranes, a clear need still exists for thin,strong filtration membranes that provide both small pore size and lowflow resistance.

SUMMARY OF THE INVENTION

The present invention is directed to novel porous PTFE membranespossessing a unique combination of high strength, low flow resistance,and small pore size. Further, the present invention is directed tounique high performance filter materials and vent constructions,including those suitable for venting applications, with filtrationperformance which has been heretofore unachievable.

Porous PTFE membranes of the present invention can be fabricated whichexhibit, for example, a combination of Gurley number versus bubble pointequal to or below the line defined by the equation log(Gurley)=5.13×10⁻³ (Bubble Point)−1.26 and a surface area of at least 20m²/g, a combination of a light transmission of a least 50% and aporosity of at least 50%, a matrix tensile strength in two orthogonaldirections of at least 1.3×10⁵ MPa², as well as various combinations ofthese unique properties. Other membranes of the invention exhibit aGurley number versus bubble point equal to or below the line defined bythe equation log (Gurley)=5.13×10⁻³ (Bubble Point)−1.58, and even equalto or below the line defined by the equation log (Gurley)=5.13×10⁻³(Bubble Point)−2.02, while still exhibiting a surface area of at least20 m²/g. Unique performance as measured by water entry pressure versusGurley number, water flux rate versus bubble point and water flux rateversus mean flow pore size are also achievable with the membranes of thepresent invention. For example, membranes with a water entry pressureversus Gurley number equal to or above the line defined by the equationWEP=3(Gurley number)+2500 have been achieved. Further, membranes with awater flux rate versus bubble point equal to or above the line definedby the equation log (water flux rate)=−3.5×10⁻³(bubble point)+1.3 havebeen made. Further, membranes with a water flux rate versus mean flowpore size equal to or above the line defined by the equation log(waterflux rate)=16.9(mean flow pore size)−1.85 are within the scope of thepresent invention.

In an alternative embodiment of the present invention, articles whichinclude composites of at least one porous PTFE membrane and at least oneadditional layer may be made. The at least one additional layer may bein the form of membranes, nonwovens, scrims and/or fabrics, depending onthe desired characteristics of the final article. For example, it ispossible to form such composite articles wherein the composites have awater flux rate versus bubble point equal to or above the line definedby the equation log (water flux rate)=−3.5×10⁻³ (bubble point)+1.3, morepreferably equal to or above the line defined by the equation log (waterflux rate)=−3.5×10⁻³ (bubble point)+1.6, and even more preferably theline defined by the equation log (water flux rate)=−3.5×10⁻³ (bubblepoint)+2.0. Alternative composite constructions may include compositesof at least one porous PTFE membrane and at least one additional layerwhere the composite is instantly wettable with water and has a waterflux rate versus bubble point equal to or above the line defined by theequation log (water flux rate)=−0.01×10⁻³ (bubble point)+1.3, morepreferably equal to or above the line defined by the equation log (waterflux rate)=−0.01×10⁻³ (bubble point)+2.48, and even more preferablyequal to or above the line defined by the equation log (water fluxrate)=−0.01×10⁻³ (bubble point)+5.0.

In a further embodiment of the invention, articles comprising porousPTFE membranes which are instantly wettable with water and which have awater flux rate versus bubble point equal to or above the line definedby the equation log (water flux rate)=−0.01×10⁻³ (bubble point)+1.3,more preferably by the equation log (water flux rate)=−0.01×10⁻³ (bubblepoint)+2.48, and most preferably by the equation log (water fluxrate)=−0.01×10⁻³ (bubble point)+5.0 can be made in accordance with thepresent invention.

In a further embodiment of the invention, articles comprising porousPTFE membranes having an oil rating of at least 2, more preferably atleast 4, and even more preferably at least 5, and a water entry pressureabove 500 kPa with a Gurley number up to 350 seconds can be made inaccordance with the teachings of the present invention. In a furtherembodiment, such oleophobic membranes can be made with a water entrypressure above 1250 kPa and a Gurley number up to 200 seconds. In aneven further embodiment, such oleophobic membranes can be made with awater entry pressure above 2000 kPa and a Gurley number up to 100seconds.

In a further embodiment of the invention, articles can be made withporous PTFE membranes having a light transmission of at least 50% and aGurley versus bubble point equal to or below the line defined by theequation log (Gurley)=5.13×10⁻³ (bubble point)−1.22, more preferablyequal to or below the line defined by the equation log(Gurley)=5.13×10⁻³ (bubble point)−1.58, and most preferably equal to orbelow the line defined by the equation log (Gurley)=5.13×10⁻³ (bubblepoint)−2.02.

Finally, filtering of fluids utilizing filters incorporating theseunique membranes and composites, including venting material as well iscontemplated herein.

These and other unique features of the invention are described herein.

DETAILED DESCRIPTION OF THE FIGURES

FIG. 1 is a graph depicting Gurley number versus bubble point for porousPTFE membranes made in accordance with examples contained herein.

FIG. 2 is a graph depicting water flux rate versus bubble point forporous PTFE membranes and composite membranes made in accordance withexamples contained herein.

FIG. 3 is a graph depicting water flux rate versus bubble point forhydrophilic porous PTFE membranes and composite membranes made inaccordance with examples contained herein.

FIG. 4 is a graph depicting water entry pressure versus Gurley numberfor oleophobic porous PTFE membranes made in accordance with examplescontained herein.

FIG. 5 is a graph depicting water entry pressure versus Gurley numberfor porous PTFE membranes made in accordance with examples containedherein.

FIG. 6 is a graph depicting water flux rate versus mean flow pore sizefor porous PTFE membranes made in accordance with examples containedherein.

DETAILED DESCRIPTION OF THE INVENTION

The porous PTFE articles of the present invention provide the surprisingcombination of high strength, low flow resistance, and small pore size.These articles fill needs for high-performance filtration media. Priorart materials suffer from either high flow resistance or low filtrationefficiency or both in comparison to materials of the present invention.Materials of the present invention provide lower flow resistance withsmaller pore size compared to prior art materials. The inventivematerials have utility in both liquid and gas filtration applications.

The combination of low flow resistance and high water entry pressuremakes the inventive materials suitable for use in gas ventingapplications, where the material allows gases and vapors to pass throughwhile repelling liquid water or other liquids.

The inventive ePTFE articles can be rendered oleophobic by varioustechniques, thereby making them fit for use in certain ventingapplications where the material has high air flow and high water entrypressure and is resistant to penetration by low surface tension fluidslike oil.

The inventive membranes can be rendered hydrophilic (water-wettableunder little or no pressure) by various techniques making them usable inliquid filtration applications which involve, for example, filtration ofaqueous fluids.

The porous PTFE membranes of this invention can be constructed ascomposite filters or composite vents, for example by layering themembrane with one or more additional layers that may provide support orprotection to the membrane. The additional layer or layers can be in theform of one or more porous membranes or more traditional air permeablematerials like knits, non-wovens, scrims, woven fabrics, etc. Dependingon the end-use requirements, an additional layer or layers may beoriented on only one side or on both sides of the membrane. Theadditional layer or layers may or may not be bonded to the membrane,depending on the end-use requirements. For example, the membrane andadditional layers may be loosely stacked, then held together byappropriate means around a perimeter of the filter, such as by ahousing, a frame, a potting compound, an adhesive, or any other suitablemeans. Alternatively, the additional layer or layers may be attached tothe membrane at a relatively few number of sites, e.g., via a suitableadhesive at locations around at least a portion of the perimeter, by adiscontinuous lamination adhesive across the surface of the layers, orany other suitable configuration meeting the requirements of the end useapplication. Suitable adhesives can include, but are not limited to,polypropylenes, polyesters, polyethylenes, PFA, FEP, and other suitableforms of thermoplastics, thermosets, and the like. Benefits of compositefilters and vents include, but are not limited to, improved handling ofthe membrane making it easier to fabricate filter cartridges or vents,improved filtration efficiency in some cases, and the like. In order toretain high flow properties of the membrane when used as a compositefilter, the additional layers are typically chosen so as to minimizeflow resistance. Also, the composite filters and vents can either behydrophobic, oleophobic, or hydrophilic depending on the application inwhich they are used.

It is generally expected based on the teachings of the prior art thatthe more a PTFE material is expanded, the larger the pore size of theresulting PTFE structure. In the case of the present invention, however,it has been unexpectedly discovered that under certain conditions it ispossible to achieve smaller pore sizes by increasing the amount ofexpansion. Even more surprising, this decrease in pore size isaccompanied by an increase in the permeability of the membrane. Theprocess results in a novel membrane structure that increasespermeability while decreasing the effective pore size. Furthermore, theresulting membrane possesses high strength.

The unique combination of permeability and pore size properties ofmembranes of the present invention is demonstrated in the graphs shownin the Figures. In these graphs, permeability is characterized by Gurleynumber or water flux rate. Increased permeability is manifested by lowerGurley numbers (i.e., less time for a given volume of air to passthrough the membrane at a given pressure), higher Frazier numbers (i.e.,the flow rate of air through the membrane for a given pressure drop andsample area), and higher water flux rates. Pore size is characterized bythe bubble point (BP), mean flow pore size, or water entry pressure(WEP) values. Higher bubble point values (the pressure required to passa bubble of air through a wetted sample of membrane) and higher WEPvalues (the pressure required to drive water droplets through amembrane) indicate smaller pore sizes. Test methods for measuring Gurleynumber, Frazier number, water flux rate, WEP, mean flow pore size, andBP are provided herein in more detail.

FIGS. 1 through 6 show the characteristics of inventive articlescompared to articles of the prior art. FIG. 1 depicts Gurley number andBP measurements for inventive and prior art membranes. The equation, log(Gurley (sec))=2.60×10⁻³ (BP (kPa))−0.54 describes the line drawn on thegraph for a bubble point greater than 448 kPa. The data points forinventive materials fall on or below this line and those for prior artmaterials fall above this line. FIG. 2 depicts water flux rate and BPmeasurements for inventive and prior art materials. The equation, log(water flux rate (cm/min/kPa))=−3.5×10⁻³ (BP (kPa))+1.3, describes theline drawn on the graph. The data points for inventive materials fall onor above this line and those for prior art materials fall below thisline. FIG. 3 depicts water flux rate and BP measurements for inventiveand prior art hydrophilic materials. The equation, log (water flux rate(cm/min/kPa))=−0.01 (BP (kPa))+1.3, describes the line drawn on thegraph. The data points for inventive materials fall on or above thisline and those for prior art materials fall below this line. FIG. 4depicts water entry pressure and Gurley number measurements forinventive and prior art oleophobic materials. The data pointscorresponding to inventive materials have water entry pressure values of500 kPa or higher and Gurley numbers of 350 sec or lower. FIG. 5 depictswater entry pressure versus Gurley number for inventive and prior artmembranes. The equation, WEP (kPa)=3(Gurley (sec))+2500, describes theline drawn on the graph. The data points for inventive materials fall onor above this line, those for prior art materials fall below this line.FIG. 6 is a graph depicting water flux rate versus mean flow pore sizefor inventive and prior art membranes. The equation, log (water fluxrate (cm/min/kPa))=16.9 (mean flow pore size (microns))−1.85, describesthe line drawn on the graph. The data points for inventive materialsfall on or above this line and those for prior art materials fall belowthis line.

In the equations provided above, Gurley number is expressed in units ofseconds, BP in units of kPa, water flux rate in units of cm/min/kPa,water entry pressure in units of kPa, and mean flow pore size in unitsof microns. The logarithmic equations utilize log to the base 10.

In these six figures, the inventive articles exhibit higher permeabilityfor a given pore size and a smaller pore size for a given permeabilityas compared to prior art articles.

The superior filtration properties of these novel membranes andcomposite articles are further enhanced by the high strength of themembranes. Not only are the present membranes strong, they are thestrongest, balanced matrix tensile strength ePTFE articles everproduced. The balance of the strength of a membrane is indicated by howclosely the ratio of the matrix tensile strengths of the membrane in twoorthogonal directions approaches unity. Balanced membranes typicallyexhibit ratios of about 2 to 1 or less. Further, these membranes possessthe largest product of matrix tensile strengths measured in twoorthogonal directions. For example, the product of matrix tensilestrengths in two orthogonal directions is greater than 1.3×10⁵ MPa² morepreferably greater than 1.5×10⁵ MPa², and even more preferably greaterthan 1.9×10⁵ MPa². Orthogonal directions include, but are not limitedto, longitudinal and transverse directions. The high strength isparticularly valuable for filtration applications in which the membraneis not used in combination with an additional layer or layers. Higherstrength also affords the use of thinner membranes. Thinner membranespresent lower flow resistance than otherwise identical thickermembranes. The high strength also facilitates the lamination of the thinmembrane to additional layers and also can improve in-use life of filtermedia in pleated forms. Furthermore, strong membranes better resistrupture in situations in which the filter is subjected to high pressuresor pulses of pressure.

Yet another surprising aspect of the invention is the unprecedented highsurface area of these novel membranes, as measured herein. Prior artePTFE membranes are referred to as having surface area per mass valuesin the range of 10 to 19 m²/g. Some membranes of the present inventioncan be tailored to have a surface area at least as high as 20 to 27m²/g.

Non-porous forms of PTFE and ePTFE allow significantly more visiblelight to pass though them than do porous, lower density forms. The indexof refraction of PTFE (typically 1.3 to 1.4 depending on percentcrystallinity of the PTFE) causes ePTFE materials to be diffuselyreflective. Typically, these materials have light transmission values ofless than 50%. Another feature of this invention is that membranespossessing high clarity can also be made which possess remarkably highdegrees of porosity. For example, membranes of the present invention canhave a light transmission of least 50% and a porosity of at least 50%.Light transmission values of 85% and higher are obtainable in membranesthat are greater than 75% porous. Such materials have particular valuein applications requiring the combination of transparency, ortranslucency, and permeability.

The present invention will be further described with respect to thenon-limiting examples provided below.

EXAMPLES

Testing Methods Utilized in the Examples

Thickness Measurements

Membrane thickness was measured by placing the membrane between the twoplates of a Kafer FZ1000/30 thickness snap gauge (Käfer MessuhrenfabrikGmbH, Villingen-Schwenningen, Germany). The average of the threemeasurements was used.

Density Measurements

Samples die cut to form rectangular sections 2.54 cm by 15.24 cm weremeasured to determine their mass (using a Mettler-Toledo analyticalbalance modelAG204) and their thickness (using a Kafer FZ1000/30 snapgauge). Using these data, density was calculated with the followingformula:

$\rho = \frac{m}{w*l*t}$in which: ρ=density (g/cc); m=mass (g); w=width (cm); l=length (cm); andt=thickness (cm). The average of the three measurements was used.Tensile Break Load Measurements and Matrix Tensile Strength (MTS)Calculations

Tensile break load was measured using an INSTRON 1122 tensile testmachine equipped with flat-faced grips and a 0.445 kN load cell. Thegauge length was 5.08 cm and the cross-head speed was 50.8 cm/min. Thesample dimensions were 2.54 cm by 15.24 cm. For longitudinal MTSmeasurements, the larger dimension of the sample was oriented in themachine, or “down web,” direction. For the transverse MTS measurements,the larger dimension of the sample was oriented perpendicular to themachine direction, also known as the cross web direction. Each samplewas weighed using a Mettler Toledo Scale Model AG204, then the thicknessof the samples was taken using the Kafer FZ1000/30 thickness snap gauge.The samples were then tested individually on the tensile tester. Threedifferent sections of each sample were measured. The average of thethree maximum load (i.e., the peak force) measurements was used. Thelongitudinal and transverse MTS were calculated using the followingequation:MTS=(maximum load/cross-section area)*(bulk density of PTFE)/density ofthe porous membrane),wherein the bulk density of PTFE is taken to be 2.2 g/cc.Ball Burst Strength Measurements

The test method and related sample mounting apparatus were developed byW.L. Gore & Associates, Inc. for use with a Chatillon Test Stand. Thetest measures the burst strength of materials such as fabrics (woven,knit, nonwoven, etc.), porous or nonporous plastic films, membranes,sheets, etc., laminates thereof, and other materials in planar form.

A specimen was mounted taut, but unstretched, between two annularclamping plates with an opening of 7.62 cm diameter. A metal rod havinga polished steel 2.54 cm diameter ball-shaped tip applied a load againstthe center of the specimen in the Z-direction (normal to the X-Y planardirections). The rod was connected at its other end to an appropriateChatillon force gauge mounted in a Chatillon Materials Test Stand, ModelNo. TCD-200. The load was applied at the rate of 25.4 cm/minute untilfailure of the specimen occurred. The failure (tearing, burst, etc.) mayoccur anywhere within the clamped area. Results were reported as theaverage of three measurements of the maximum applied force beforefailure.

Testing was done at ambient interior temperature and humidityconditions, generally at a temperature of 21 to 24° C. and relativehumidity of 35 to 55%. Ball burst data can be expressed as the ballburst strength as a function of mass per area of the sample; mass perarea of the sample can be determined from the product of density andthickness of the sample.

Gurley Measurements

The Gurley air flow test measures the time in seconds for 100 cm³ of airto flow through a 6.45 cm² sample at 12.4 cm of water pressure. Thesamples were measured in a Gurley Densometer Model 4340 AutomaticDensometer. Articles possessing Gurley values less than about 2 secondswere submitted for Frazier number testing, since this test provides morereliable values for the characterization of highly permeable articles.The average of the three measurements was used.

Frazier Measurements

The Frazier permeability reading is the rate of flow of air in cubicfeet per square foot of sample area per minute at a differentialpressure drop across the test sample of 12.7 mm water column. Airpermeability was measured by clamping a test sample into a circulargasketed flanged fixture which provided a circular opening of 17.2 cmdiameter (232 cm² area). The upstream side of the sample fixture wasconnected to a flow meter in line with a source of dry compressed air.The downstream side of the sample fixture was open to the atmosphere.The flow rate through the sample was measured and recorded as theFrazier number. The average of the three measurements was used. Fraziernumber data can be converted to Gurley numbers by use of the followingequation: Gurley=3.126/Frazier, in which Gurley number is expressed inunits of seconds.

Water Flux Rate Measurement

The following procedure was used to calculate the water flux ratethrough the membrane. The membrane was either draped across the tester(Sterifil Holder 47 mm Catalog Number: XX11J4750, Millipore) or cut tosize and laid over the test plate. The membrane was first wet outcompletely with 100% isopropyl alcohol. The tester was filled withde-ionized water (room temperature). A pressure of 33.87 kPa was appliedacross the membrane; the time for 400 cm³ of de-ionized water to flowthrough the membrane was measured. The water flux rate was thencalculated using the following equation:water flux rate [cm/min/kPa]=water flow rate [cm³/min]/sample area[cm²]/test pressure [kPa].

It should be noted that for hydrophilic membranes, the membrane was notpre-wet with isopropyl alcohol. The same procedure outlined above wasused to measure water flux rate through composite filters. The averageof the three measurements was used.

Water Entry Pressure Measurement

Water entry pressure is a test method for measuring water intrusionthrough a membrane. A Mullen® Tester (Serial No: 8240+92+2949,manufactured by BF. Perkins, Chicopee, Mass., USA) was used. A testsample was clamped between a pair of testing fixtures made of 1.27 cmthick square plexiglass sheets, 10.16 cm long on each side. The lowerfixture had the ability to pressurize a section of the sample withwater. A piece of pH paper was placed on top of the sample to serve asan indicator of evidence for water entry. The sample was thenpressurized in small increments of pressure until a color change in thepH paper was noticed. The corresponding breakthrough pressure or entrypressure was recorded as the water entry pressure. The average of thethree measurements was used.

Bubble Point Measurements

The bubble point and mean flow pore size were measured according to thegeneral teachings of ASTM F31 6-03 using a Capillary Flow Porometer(Model CFP 1500 AEXL from Porous Materials Inc., Ithaca, N.Y.). Thesample membrane was placed into the sample chamber and wet with SilWickSilicone Fluid (available from Porous Materials Inc.) having a surfacetension of 19.1 dynes/cm. The bottom clamp of the sample chamber had a2.54 cm diameter, 3.175 mm thick porous metal disc insert (MottMetallurgical, Farmington, Conn., 40 micron porous metal disk) and thetop clamp of the sample chamber had a 3.175 mm diameter hole. Using theCapwin software version 6.62.1 the following parameters were set asspecified in the table immediately below. The values presented forbubble point and mean flow pore size were the average of twomeasurements.

Parameter Set Point maxflow (cc/m) 200000 bublflow (cc/m) 100 F/PT (oldbubltime) 40 minbppres (PSI) 0 zerotime (sec) 1 v2incr (cts) 10 preginc(cts) 1 pulse delay (sec) 2 maxpre (PSI) 500 pulse width (sec) 0.2mineqtime (sec) 30 presslew (cts) 10 flowslew (cts) 50 eqiter 3 aveiter20 maxpdif (PSI) 0.1 maxfdif (cc/m) 50 sartp (PSI) 1 sartf (cc/m) 500Light Transmission Measurements

A radiometer (Model IC 1700, International Light, Newburyport, Mass.)was used to measure the amount of light transmission through the samplesof ePTFE membrane. A black tube, approximately the same diameter as theouter diameter of the light receiving sensor, Model SED 033, was clampedonto the light sensor and protruded approximately 13.3 cm from thereceiving face of the sensor. The light source, a Sylvania Reflector 50W, 120V bulb, was mounted directly across from the light sensorapproximately 28.6 cm from the receiving face of the light sensor. Theradiometer was calibrated by placing a cap over the end of the tubeprotruding from the light sensor to set the zero point, and removing thecap and turning on the light source with nothing between the lightsource and the light sensor to set the 100% point. After calibrating theradiometer, the ePTFE membrane was mounted into a 25.4 cm diameterembroidery hoop and held between the light source and the light sensor,approximately 7.6 cm from the light source. The percent transmission oflight displayed on the IC 1700 radiometer was recorded. The average ofthe three measurements was used.

Surface Area Measurements

The surface area per unit mass, expressed in units of m²/g, of the ePTFEmembrane was measured using the Brunauer-Emmett-Teller (BET) method on aCoulter SA3100 Gas Adsorption Analyzer (Beckman Coulter Inc., Fullerton,Calif.). A sample was cut from the center of the ePTFE membrane sheetand placed into a small sample tube (reference number 8201151). The massof the ePTFE sample was approximately 0.1 to 0.2 grams. The tube wasplaced into the Coulter SA-Prep Surface Area Outgasser, (Model SA-PREP,P/N 5102014) from Beckman Coulter Inc., Fullerton, Calif. and purged at110 C for 2 hours with helium. The sample tube was then removed from theSA-Prep Outgasser and weighed. The sample tube was then placed into theSA3100 Gas Adsorption Analyzer and the BET surface area analysis was runin accordance with the instrument instructions using helium to calculatethe free space and nitrogen as the adsorbate gas. A single measurementwas recorded for each sample.

Porosity Calculations

Porosity was expressed in percent porosity and was determined bysubtracting the quotient of the average density of the article(described earlier herein) and that of the bulk density of PTFE from 1,then multiplying that value by 100%. For the purposes of thiscalculation, the bulk density of PTFE was taken to be 2.2 g/cc.

Oil Repellency Measurement/Oil Rating

Oil rating was measured using the AATCC Test Method 118-1997. The oilrating of a membrane is the lower of the two ratings obtained whentesting the two sides of the membrane. The higher the number, the betterthe oil repellency.

Water-Wettability Measurement

Water-wettability was measured in order to characterize the degree ofhydrophilicity of a sample. The sample was held taught in a 10.16 cmdiameter hoop. A single droplet of water was dropped from a height of 5cm directly above the sample onto the sample. The time for the dropletto penetrate the pores of the sample was measured. The degree ofwater-wettability was defined using the following scale:

-   0=water droplet penetrated the sample within 5 seconds-   1=water droplet penetrated the sample after greater than 5 seconds    and less than 60 seconds-   2=water drop did not penetrate the sample after 60 seconds.

Hydrophobic materials such as porous ePTFE materials possessingrelatively small pores typically exhibit water-wettability ratings of 2.Materials exhibiting water-wettability ratings of 0 or 1 were consideredto be instantly wettable.

Example 1

Fine powder of PTFE polymer (Daikin Industries, Ltd., Orangeburg, N.Y.)was blended with Isopar K (Exxon Mobil Corp., Fairfax, Va.) in theproportion of 0.196 g/g of fine powder. The lubricated powder wascompressed in a cylinder to form a pellet and placed into an oven set at70° C. for approximately 12 hours. Compressed and heated pellets wereram extruded to produce tapes approximately 15.2 cm wide by 0.73 mmthick. Three separate rolls of tape were produced and layered togetherbetween compression rolls to a thickness of 0.76 mm. The tape was thentransversely stretched to 56 cm (i.e., at a ratio of 3.7:1), restrained,then dried in an oven set at 270° C. The dry tape was longitudinallyexpanded between banks of rolls over a heated plate set to a temperatureof 340° C. The speed ratio between the second bank of rolls and thefirst bank of rolls, and hence the expansion ratio, was 8:1. Thelongitudinally expanded tape was then expanded transversely at atemperature of approximately 320° C. to a ratio of 34:1 and thenconstrained and heated in an oven set at 320° C. for approximately 24seconds. The process conditions and intermediate article dimensions forthis example appear in Table 1. The process produced a thin strongporous membrane.

TABLE 1 Process Conditions & Intermediate Article Dimensions Example 1Example 2 Example 3 Example 4 Example 5 lubrication level (g/g of resin)0.196 0.196 0.202 0.196 0.202 pellet conditioning - time (hr) 12 12 1212 12 pellet conditioning - temperature set 70 70 70 70 70 point (degC.) tape width (cm) 15.2 15.2 15.2 15.2 15.2 tape thickness (mm) 0.730.73 0.73 0.73 0.73 number of tape layers 3 3 3 1 3 calendered tapethickness (mm) 0.76 0.76 0.76 0.25 0.76 transverse stretch ratio 3.7:1 3.7:1  3.7:1  3.7:1  3.7:1  drying temperature set point (deg C.) 270270 250 270 250 expansion temperature set point (deg 340 340 345 345 345C.) longitudinal expansion ratio  8:1 13:1 15:1 15:1 20:1 expansiontemperature set point (deg 320 320 360 360 360 C.) transverse expansionratio 34:1 32:1 30:1 30:1 22:1 heat treatment temperature set point 320320 390 380 390 (deg C.) heat treatment time (sec) 24 24 20 24 20

This membrane was then characterized by measuring various properties inthe manners described above. Membrane properties for the sample made inthis example appear in Table 2. Gurley number and BP data for the sampleof this example appear in FIG. 1. Water flux rate and BP data for thesample of this example appear in FIG. 2. Water entry pressure and Gurleynumber data for the sample of this example appear in FIG. 5. Water fluxrate and mean flow pore size data for the sample of this example appearin FIG. 6.

TABLE 2 Membrane Property Example 1 Example 2 Example 3 Example 4Example 5 density (g/cc) 0.357 0.339 0.348 0.294 0.358 thickness (mm)0.020 0.013 0.010 0.0025 0.0076 longitudinal MTS 217 312 471 414 584(MPa) transverse MTS 214 249 289 460 229 (MPa) product of longitudinal46,570 77,568 136,042 190,562 133,539 and transverse MTS (MPa{circumflexover ( )}2) ball burst strength (N) 21.3 18.0 45.4 16.5 35.1 GurleyNumber (sec) 11.1 7.6 12.5 2.1 7.3 Bubble point (kPa) 647 564 877 605764 water flux rate 0.23 0.33 0.12 0.61 0.25 (cm/min/kPa) mean flow poresize 0.056 0.065 0.05545 0.0765 0.0642 (micron) water entry pressure3111 2939 ≧4136 (kPa) surface area (m{circumflex over ( )}2/g) 17.2 18.427.4 23.5

Example 2

Fine powder of PTFE polymer (Daikin Industries, Ltd., Orangeburg, N.Y.)was blended with Isopar K (Exxon Mobil Corp., Fairfax, Va.) in theproportion of 0.196 g/g of fine powder. The lubricated powder wascompressed in a cylinder to form a pellet and placed into an oven set at70° C. for approximately 12 hours. The compressed and heated pelletswere ram extruded to produce tapes approximately 15.2 cm wide by 0.73 mmthick. Three separate rolls of tape were produced and layered togetherbetween compression rolls to a thickness of 0.76 mm. The tape was thentransversely stretched to 56 cm (i.e., at a ratio of 3.7:1), restrained,then dried at a temperature of 270° C. The dry tape was longitudinallyexpanded between banks of rolls in a heat zone set to a temperature of340° C. The speed ratio between the second bank of rolls to the firstbank of rolls, and hence the expansion ratio, was 13:1. Thelongitudinally expanded tape was then expanded transversely at atemperature of approximately 320° C. to a ratio of 32:1 and thenrestrained and heated to 320° C. for approximately 24 seconds. Theprocess conditions and intermediate article dimensions for this exampleappear in Table 1. The process produced a thin strong porous membrane.

This membrane was then characterized by measuring various properties inthe manners described above. Membrane properties for the sample made inthis example appear in Table 2. Gurley number and BP data for the sampleof this example appear in FIG. 1. Water flux rate and BP data for thesample of this example appear in FIG. 2. Water entry pressure and Gurleynumber data for the sample of this example appear in FIG. 5. Water fluxrate and mean flow pore size data for the sample of this example appearin FIG. 6.

Example 3

Fine powder of PTFE polymer as described and taught in U.S. Pat. No.6,541,589 was blended with Isopar K (Exxon Mobil Corp., Fairfax, Va.) inthe proportion of 0.202 g/g of fine powder. The lubricated powder wascompressed into a cylinder to form a pellet and placed into an oven setat 70° C. for approximately 12 hours. Compressed and heated pellets wereram extruded to produce tapes approximately 15.2 cm wide by 0.73 mmthick. Three separate rolls of tape were produced and layered togetherbetween compression rolls to a thickness of 0.76 mm. The tape was thentransversely stretched to 56 cm (i.e., at a ratio of 3.7:1), restrained,then dried at a temperature of 250° C. The dry tape was longitudinallyexpanded between banks of rolls over a heated plate set to a temperatureof 345° C. The speed ratio between the second bank of rolls and thefirst bank of rolls was 15:1. The longitudinally expanded tape was thenexpanded transversely at a temperature of approximately 360° C. to aratio of 30:1 and then restrained and heated in an oven set at 390° C.for approximately 20 seconds. The process produced a thin strong porousmembrane. The process conditions and intermediate article dimensions forthis example appear in Table 1.

This membrane was then characterized by measuring various properties inthe manners described above. Membrane properties for the sample made inthis example appear in Table 2. Note that the water entry pressure wasat least 4136 kPa because the tester was unable to measure higher thanthat. Gurley number and BP data for the sample of this example appear inFIG. 1. Water flux rate and BP data for the sample of this exampleappear in FIG. 2. Water flux rate and mean flow pore size data for thesample of this example appear in FIG. 6.

Example 4

Fine powder of PTFE polymer as described and taught in U.S. Pat. No.6,541,589 was blended with Isopar K (Exxon Mobil Corp., Fairfax, Va.) inthe proportion of 0.196 g/g of fine powder. The lubricated powder wascompressed into a cylinder to form a pellet and placed into an oven setat 70° C. for approximately 12 hours. The compressed and heated pelletwas ram extruded to produce a tape approximately 15.2 cm wide by 0.73 mmthick. The extruded tape was then rolled down between compression rollsto a thickness of 0.254 mm. The tape was then transversely stretched to56 cm (i.e., at a ratio of 3.7:1), restrained, then dried at atemperature of 270° C. The dry tape was longitudinally expanded betweenbanks of rolls over a heated plate set to a temperature of 345° C. Thespeed ratio between the second bank of rolls and the first bank of rollswas 15:1. The longitudinally expanded tape was then expandedtransversely at a temperature of approximately 360° C. to a ratio of30:1 and then restrained and heated in an oven set at 380° C. forapproximately 24 seconds. The process produced a thin strong porousmembrane. The process conditions and intermediate article dimensions forthis example appear in Table 1.

This membrane was then characterized by measuring various properties inthe manners described above. Membrane properties for the sample made inthis example appear in Table 2. Light transmission was measured to be90%. Gurley number and BP data for the sample of this example appear inFIG. 1. Water flux rate and BP data for the sample of this exampleappear in FIG. 2. Water flux rate and mean flow pore size data for thesample of this example appear in FIG. 6.

Example 5

Fine powder of PTFE polymer as described and taught in U.S. Pat. No.6,541,589 was blended with Isopar K (Exxon Mobil Corp., Fairfax, Va.) inthe proportion of 0.202 g/g of fine powder. The lubricated powder wascompressed into a cylinder to form a pellet and placed into an oven setat 70° C. for approximately 12 hours. Compressed and heated pellets wereram extruded to produce tapes approximately 15.2 cm wide by 0.73 mmthick. Three separate rolls of tape were produced and layered togetherbetween compression rolls to a thickness of 0.76 mm. The tape was thentransversely stretched to 56 cm (i.e., at a ratio of 3.7:1), restrained,then dried at a temperature of 250° C. The dry tape was longitudinallyexpanded between banks of rolls in a heat zone set to a temperature of345° C. The speed ratio between the second bank of rolls and the firstbank of rolls was 20:1. The longitudinally expanded tape was thenexpanded transversely at a temperature of approximately 360° C. to aratio of 22:1 and then restrained and heated to 390° C. forapproximately 20 seconds. The process produced a thin strong porousmembrane. The process conditions and intermediate article dimensions forthis example appear in Table 1.

This membrane was then characterized by measuring various properties inthe manners described above. Membrane properties for the sample made inthis example appear in Table 2. Gurley number and BP data for the sampleof this example appear in FIG. 1. Water flux rate and BP data for thesample of this example appear in FIG. 2. Water flux rate and mean flowpore size data for the sample of this example appear in FIG. 6.

Example 6

The membrane of Example 1 was treated to render it hydrophilic accordingto the following procedure. The membrane sample was held taut in a hoop(10.16 cm diameter). A solution was prepared by dissolving 1% polyvinylalcohol (Catalog Number 363170, Sigma-Aldrich Co) in a 50/50 mixture ofisopropyl alcohol/deionized water. The hoop was immersed in thissolution for 1 minute and then rinsed in deionized water for anotherminute. The hoop was then immersed in a solution containing 2%glutaraldehyde (Catalog Number 340855, Sigma-Aldrich Co), 1%hydrochloric acid (Catalog Number 435570, Sigma-Aldrich Co) in deionizedwater for 1 minute. The solution temperature was maintained at 50 deg C.This was followed by a deionized water rinse for 1 minute. Finally, thesample was dried in an oven set to 150 deg C. The sample was removedfrom the oven when it was completely dry. The resulting sample wasinstantaneously water-wettable, as it exhibited a water-wettabilityrating of 0. Bubble point and water flux rate values of the hydrophilicmembrane made in this example were 697 kPa and 0.03 cm/min/kPa,respectively. Water flux rate and BP data for the sample of this exampleappear in FIG. 3.

Example 7

The membrane of Example 2 was treated to render it hydrophilic accordingto the following procedure. The membrane sample was held taut in a hoop(10.16 cm diameter). A solution was prepared by dissolving 1% polyvinylalcohol (Catalog Number 363170, Sigma-Aldrich Co) in a 50/50 mixture ofisopropyl alcohol/deionized water. The hoop was immersed in thissolution for 1 minute and then rinsed in deionized water for anotherminute. The hoop was then immersed in a solution containing 2%glutaraldehyde (Catalog Number 340855, Sigma-Aldrich Co), and 1%hydrochloric acid (Catalog Number 435570, Sigma-Aldrich Co) in deionizedwater for 1 minute. The solution temperature was maintained at 50 deg C.This was followed by a deionized water rinse for 1 minute. Finally, thesample was dried in an oven set to 150 deg C. The sample was removedfrom the oven when it was completely dry. The resulting sample wasinstantaneously water-wettable, as it exhibited a water-wettabilityrating of 0. Bubble point and water flux rate values of the hydrophilicmembrane made in this example were 672 kPa and 0.05 cm/min/kPa,respectively. Water flux rate and BP data for the sample of this exampleappear in FIG. 3.

Example 8

The membrane of Example 4 was treated to render it hydrophilic accordingto the following procedure. The membrane sample was held taut in a hoop(10.16 cm diameter). A solution was prepared by dissolving 1% polyvinylalcohol (Catalog Number 363170, Sigma-Aldrich Co) in a 50/50 mixture ofisopropyl alcohol/deionized water. The hoop was immersed in thissolution for 1 minute and then rinsed in deionized water for anotherminute. The hoop was then immersed in a solution containing 2%glutaraldehyde (Catalog Number 340855, Sigma-Aldrich Co), and 1%hydrochloric acid (Catalog Number 435570, Sigma-Aldrich Co) in deionizedwater for 1 minute. The solution temperature was maintained at 50 deg C.This was followed by a deionized water rinse for 1 minute. Finally, thesample was dried in an oven at 150 deg C. The sample was removed fromthe oven when it was completely dry. The resulting sample wasinstantaneously water-wettable, it exhibited a water-wettability ratingof 0. Bubble point and water flux rate values of the hydrophilicmembrane made in this example were 760 kPa and 0.1 cm/min/kPa,respectively. Water flux rate and BP data for the sample of this exampleappear in FIG. 3.

Example 9

Fine powder of PTFE polymer (Daikin Industries, Ltd., Orangeburg, N.Y.)was blended with Isopar K (Exxon Mobil Corp., Fairfax, Va.) in theproportion of 0.196 g/g of fine powder. The lubricated powder wascompressed in a cylinder to form a pellet and placed into an oven set at70° C. for approximately 12 hours. Compressed and heated pellets wereram extruded to produce tapes approximately 15.2 cm wide by 0.73 mmthick. Three separate rolls of tape were produced and layered togetherbetween compression rolls to a thickness of 0.76 mm. The tape was thentransversely stretched to 56 cm (i.e., at a ratio of 3.7:1), restrained,then dried in an oven set at 270° C. The dry tape was longitudinallyexpanded between banks of rolls over a heated plate set to a temperatureof 340° C. The expansion ratio was calculated as the ratio between thespeeds of the two banks of rolls and was determined to be 25:1. Thelongitudinally expanded tape was then expanded transversely at atemperature of approximately 360° C. to a ratio of 20:1 and thenrestrained and heated in an oven set at 390° C. for approximately 60seconds. The process produced a thin strong porous membrane.

The membrane had the following properties: a thickness of 0.0051 mm, adensity of 0.334 g/cc, longitudinal matrix tensile strength of 546 MPa,transverse matrix tensile strength of 276 MPa, ball burst strength of22.7 N, Frazier number of 2.8, bubble point of 317 kPa, water flux rateof 1.72 cm/min/kPa, mean flow pore size of 0.101 microns, and a surfacearea of 24.8 m²/g. Water flux rate and BP data for this membrane appearin FIG. 2. Water flux rate and mean flow pore size data for thismembrane appear in FIG. 6.

The membrane was treated to render it hydrophilic according to thefollowing procedure. The membrane sample was held taut in a hoop (10.16cm diameter). A solution was prepared by dissolving 1% polyvinyl alcohol(Catalog Number 363170, Sigma-Aldrich Co) in a 50/50 mixture ofisopropyl alcohol/deionized water. The hoop was immersed in thissolution for 1 minute and then rinsed in deionized water for anotherminute. The hoop was then immersed in a solution containing 2%glutaraldehyde (Catalog Number 340855, Sigma-Aldrich Co), and 1%hydrochloric acid (Catalog Number 435570, Sigma-Aldrich Co) in deionizedwater for 1 minute. The solution temperature was maintained at 50 deg C.This was followed by a deionized water rinse for 1 minute. Finally, thesample was dried in an oven set to 150 deg C. The sample was removedfrom the oven when it was dry. The resulting sample was instantaneouslywater-wettable, as it exhibited a water-wettability rating of 0. Bubblepoint and water flux rate values of the hydrophilic membrane made inthis example were 312 kPa and 0.42 cm/min/kPa, respectively. Water fluxrate and BP data for the treated membrane of this example appear in FIG.3.

Example 10

The hydrophilic membrane of Example 7 was constructed as a compositehydrophilic filter by layering the membrane between two other layers.

These outer layers were ePTFE membranes possessing a Frazier number of40 which were subsequently hydrophilized. These two layers served ascover layers (i.e., a layer which covers at least a portion of thesurface of the membrane); they had very high fluid permeability suchthat the resultant assembled composite hydrophilic filter possessedessentially the same permeability as the hydrophilic membrane of Example7. The outer, or cover, layer membranes were rendered hydrophilic usingthe following procedure. Each cover layer membrane was held taut in ahoop (10.16 cm diameter). A solution was prepared by dissolving 1%polyvinyl alcohol (Catalog Number 363170, Sigma-Aldrich Co) in a 50/50mixture of isopropyl alcohol/deionized water. The hoop was immersed inthis solution for 1 minute and then rinsed in deionized water foranother minute. The hoop was then immersed in a solution containing 2%glutaraldehyde (Catalog Number 340855, Sigma-Aldrich Co), and 1%hydrochloric acid (Catalog Number 435570, Sigma-Aldrich Co) in deionizedwater for 1 minute. The solution temperature was maintained at 50 deg C.This was followed by a deionized water rinse for 1 minute. Finally, eachcover layer was dried in an oven set to 150 deg C. The sample wasremoved from the oven when it was dry.

At this point, the composite hydrophilic filter was assembled byorienting in a layered, but unbonded, configuration the hydrophilicmembrane of Example 7 between the two hydrophilic cover membranes. Thus,the composite filter consisted of three layers loosely stacked on top ofeach other. The edges of the composite were sealed as needed in the testfixtures. Bubble point and water flux rate values of the hydrophiliccomposite were 678 kPa and 0.06 cm/min/kPa, respectively. The compositewas instantaneously water-wettable, as it exhibited a water-wettabilityrating of 0. Water flux rate and BP data for the sample of this exampleappear in FIG. 3. Note the proximity of the data point for the compositearticle relative to the data point for the membrane (of Example 7) usedin constructing the composite. The similar properties of the membraneand the composite attest to how well the properties of the membrane canbe preserved in the final composite article.

Example 11

The hydrophilic membrane of Example 8 was constructed as a compositehydrophilic filter by layering the membrane between two other layers.These two outer, or cover, layers were created in the same manner asdescribed in Example 10.

The composite hydrophilic filter was assembled by orienting in alayered, but unbonded, configuration the hydrophilic membrane of Example8 between the two hydrophilic cover membranes. Thus, the compositefilter consisted of three layers loosely stacked on top of each other.The edges of the composite were sealed as needed in the test fixtures.Bubble point and water flux rate values of the hydrophilic compositemade in this example were 705 kPa and 0.09 cm/min/kPa, respectively. Thecomposite was instantaneously water-wettable, as it exhibited awater-wettability rating of 0. Water flux rate and BP data for thesample of this example appear in FIG. 3. Note the proximity of the datapoint for the composite article relative to the data point for themembrane (of Example 8) used in constructing the composite. The similarproperties of the membrane and the composite attest to how well theproperties of the membrane can be preserved in the final compositearticle.

Example 12

The hydrophilic membrane of Example 9 was used to construct a compositehydrophilic filter by layering the membrane between two other layers.These two outer, or cover, layers were created in the same manner asdescribed in Example 10.

At this point, the composite hydrophilic filter was assembled byorienting in a layered, but unbonded, configuration the hydrophilicmembrane of Example 9 between the two hydrophilic cover membranes.During testing, the edges of the composite were clamped, as appropriate,to perform the test. Thus, the composite filter consisted of threelayers loosely stacked on top of each other. The edges of the compositewere sealed as needed in the test fixtures. The composite wasinstantaneously water-wettable, as it exhibited a water-wettabilityrating of 0. Water flux rate and BP data for the sample of this exampleappear in FIG. 3. Note the proximity of the data point for the compositearticle relative to the data point for the membrane (of Example 9) usedin constructing the composite. The similar properties of the membraneand the composite attest to how well the properties of the membrane canbe preserved in the final composite article.

Example 13

The membrane of Example 1 was treated to render it oleophobic accordingto the teachings of Example 1 of U.S. Pat. No. 5,116,650. The resultingmembrane had an oil rating of 3. Water entry pressure and Gurley valuesfor the oleophobic membrane made in this example were 2447 kPa and 34sec, respectively. Water entry pressure and Gurley number data for thesample of this example appear in FIG. 4.

Example 14

The membrane of Example 2 was treated to render it oleophobic accordingto the teachings of Example 1 of U.S. Pat. No. 5,116,650. This membranehad an oil rating of 3. Water entry pressure and Gurley values for theoleophobic membrane made in this example were 2530 kPa and 22 sec,respectively. Water entry pressure and Gurley number data for the sampleof this example appear in FIG. 4.

Example 15

The membrane of Example 2 was used to construct a composite filter bylayering the membrane between two other layers. These two outer, orcover, layers were ePTFE membranes possessing a Frazier number of 40.These two layers served as cover layers; they had very high fluidpermeability such that the resultant composite filter possessedessentially the same permeability as the membrane of Example 2.

The composite filter was assembled by orienting in a layered, butunbonded, configuration the membrane of Example 2 between the two covermembranes. Thus, the composite filter consisted of three layers looselystacked on top of each other. The edges of the composite were sealed asneeded in the test fixtures. Bubble point and water flux rate values forthe composite filter were 556 kPa and 0.37 cm/min/kPa, respectively.Water flux rate and BP data for the sample of this example appear inFIG. 2. Note the proximity of the data point for the composite articlerelative to the data point for the membrane (of Example 2) used inconstructing the composite. The similar properties of the membrane andthe composite attest to how well the properties of the membrane can bepreserved in the final composite article.

Example 16

The membrane of Example 4 was used to construct a composite filter bylayering the membrane between two other layers. These outer layers wereePTFE membranes possessing a Frazier number of 40. These two layersserved as cover layers; they had very high fluid permeability such thatthe resultant composite filter possessed essentially the samepermeability as the membrane of Example 4.

The composite filter was assembled by orienting in a layered, butunbonded, configuration the membrane of Example 4 between the two covermembranes. Thus, the composite filter consisted of three layers looselystacked on top of each other. The edges of the composite were sealed asneeded in the test fixtures. Bubble point and water flux rate values forthe composite filter were 575 kPa and 0.66 cm/min/kPa, respectively.Water flux rate and BP data for the sample of this example appear inFIG. 2. Note the proximity of the data point for the composite articlerelative to the data point for the membrane (of Example 4) used inconstructing the composite. The similar properties of the membrane andthe composite attest to how well the properties of the membrane can bepreserved in the final composite article.

Example 17

Fine powder of PTFE polymer as described and taught in U.S. Pat. No.6,541,589 was blended with Isopar K (Exxon Mobil Corp., Fairfax, Va.) inthe proportion of 0.196 g/g of fine powder. The lubricated powder wascompressed into a cylinder to form a pellet and placed into an oven setat 70° C. for approximately 12 hours. The compressed and heated pelletwas ram extruded to produce a tape approximately 15.2 cm wide by 0.73 mmthick. The extruded tape was then rolled down between compression rollsto a thickness of 0.19 mm. The tape was then transversely stretched to56 cm (i.e., at a ratio of 3.7:1) then dried at a temperature of 250° C.The dry tape was longitudinally expanded between banks of rolls over aheated plate set to a temperature of 340° C. The speed ratio between thesecond bank of rolls and the first bank of rolls was 20:1. Thelongitudinally expanded tape was then expanded transversely at atemperature of approximately 360° C. to a ratio of 20:1 and thenrestrained and heated in an oven set at 400° C. for approximately 180seconds.

The process produced a thin strong porous membrane. The membrane had thefollowing properties: a thickness of 0.0025 mm, a density of 0.180 g/cc,longitudinal matrix tensile strength of 609 MPa, transverse matrixtensile strength of 220 MPa, ball burst strength of 3.6 N, Fraziernumber of 6.1, bubble point of 337 kPa, water flux rate of 2.49cm/min/kPa, mean flow pore size of 0.085 microns, and a lighttransmission of 92%. Water flux rate and mean flow pore size data forthis membrane appear in FIG. 6.

This membrane was used to construct a composite filter by layering themembrane between two other layers. These outer layers were ePTFEmembranes possessing a Frazier number of 40. These two layers served ascover layers; they had very high fluid permeability such that theresultant composite filter possessed essentially the same permeabilityas the membrane made earlier in this example.

The composite filter was assembled by orienting in a layered, butunbonded, configuration this membrane between the two cover membranes.Thus, the composite filter consisted of three layers were looselystacked on top of each other. The edges of the composite were sealed asneeded in the test fixtures. Bubble point and water flux rate values forthe composite filter were 374 kPa and 1.92 cm/min/kPa, respectively.Water flux rate and BP data for the membrane and the composite articleof this example appear in FIG. 2. Note the proximity of the data pointfor the composite article relative to the data point for the membraneused in constructing the composite. The similar properties of themembrane and the composite attest to how well the properties of themembrane made in this example can be preserved in the final compositearticle.

While the invention has been disclosed herein in connection with certainembodiments and detailed descriptions, it will be clear to one skilledin the art that modifications or variations of such detail can be madewithout deviating from the spirit of the invention, and suchmodifications or variations are considered to be within the scope of theclaims herein.

1. An article comprising a porous PTFE membrane formed by a methodcomprising forming an extruded lubricated tape of PTFE polymer by apaste extrusion process; stretching the extruded lubricated tapetransversely, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape; then transversely expandingthe tape at an expansion ratio of 20:1 or greater, said porous PTFEmembrane having a Gurley versus bubble point equal to or below the linedefined by the equation log (Gurley)=5.13×10⁻³ (Bubble Point)−1.26 and asurface area of at least 20 m²/g.
 2. The article of claim 1, whereinsaid extruded lubricated tape is stretched transversely at a ratio of atleast 3:1.
 3. The article of claim 1, wherein the ratio of matrixtensile strength in two orthogonal directions is 2:1 or less.
 4. Thearticle of claim 1, wherein the product of matrix tensile strength intwo orthogonal directions is greater than 1.3×10⁵ MPa².
 5. The articleof claim 1, wherein the product of matrix tensile strength in twoorthogonal directions is greater than 1.5×10⁶ MPa².
 6. The article ofclaim 1, wherein the product of matrix tensile strength in twoorthogonal directions is greater than 1.9×10⁵ MPa².
 7. The article ofclaim 1, wherein said PTFE membrane has a light transmission of greaterthan 50%.
 8. The article of claim 1, wherein the Gurley versus bubblepoint is equal to or below the line defined by the equation log(Gurley)=5.13×10⁻³ (Bubble Point)−1.58.
 9. The article of claim 1,wherein the Gurley versus bubble point is equal to or below the linedefined by the equation log (Gurley)=5.13×10⁻³ (Bubble Point)−2.02. 10.An article comprising a porous PTFE membrane formed by a methodcomprising forming an extruded lubricated tape of PTFE polymer by apaste extrusion process; stretching the extruded lubricated tapetransversely, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape; then transversely expandingthe tape at an expansion ratio of 20:1 or greater, said porous PTFEmembrane having a light transmission of at least 50% and a porosity ofat least 50%.
 11. The article of claim 10, wherein said extrudedlubricated tape is stretched transversely at a ratio of at least 3:1.12. The article of claim 10, wherein said porous PTFE membrane has alight transmission of at least 85% and a porosity of at least 75%. 13.An article comprising a porous PTFE membrane formed by a methodcomprising forming an extruded lubricated tape of PTFE polymer by apaste extrusion process; stretching the extruded lubricated tapetransversely, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape; then transversely expandingthe tape at an expansion ratio of 20:1 or greater, said porous PTFEmembrane having a bubble point of at least 448 kPa and a Gurley versusbubble point equal to or below the line defined by the equation log(Gurley)=2.60×10⁻³ (Bubble Point)−0.54.
 14. The article of claim 13,wherein said extruded lubricated tape is stretched transversely at aratio of at least 3:1.
 15. The article of claim 13, wherein the Gurleyversus bubble point is equal to or below the line defined by theequation log (Gurley)=2.60×10⁻³ (Bubble Point)−0.59.
 16. The article ofclaim 13, wherein the Gurley versus bubble point is equal to or belowthe line defined by the equation log (Gurley)=2.60×10⁻³ (BubblePoint)−1.12.
 17. A porous PTFE membrane formed by a method comprisingforming an extruded lubricated tape of PTFE polymer by a paste extrusionprocess; stretching the extruded lubricated tape transversely, anddrying the stretched tape to remove lubricant; longitudinally expandingthe resulting tape; then transversely expanding the tape at an expansionratio of 20:1 or greater, said porous PTFE membrane having a product ofmatrix tensile strengths in two orthogonal directions of at least1.3×10⁵ MPa².
 18. The article of claim 17, wherein said extrudedlubricated tape is stretched transversely at a ratio of at least 3:1.19. The article of claim 17, wherein the product of matrix tensilestrength in two orthogonal directions is greater than 1.5×10⁵ MPa². 20.The article of claim 17, wherein the product of matrix tensile strengthin two orthogonal directions is greater than 1.9×10⁵ MPa².
 21. Anarticle comprising a porous PTFE membrane formed by a method comprisingforming an extruded lubricated tape of PTFE polymer by a paste extrusionprocess; stretching the extruded lubricated tape transversely, anddrying the stretched tape to remove lubricant; longitudinally expandingthe resulting tape; then transversely expanding the tape at an expansionratio of 20:1 or greater, said porous PTFE membrane having a Gurleyversus bubble point equal to or below the line defined by the equationlog (Gurley)=5.13×10⁻³ (Bubble Point)−1.26 and a product of matrixtensile strengths in two orthogonal directions of at least 1.3×10⁵ MPa².22. The article of claim 21, wherein said extruded lubricated tape isstretched transversely at a ratio of at least 3:1.
 23. The article ofclaim 21, wherein the product of matrix tensile strength in twoorthogonal directions is greater than 1.5×10⁵.
 24. The article of claim21, wherein the product of matrix tensile strength in two orthogonaldirections is greater than 1.9×10⁵.
 25. The article of claim 21, whereinthe Gurley versus bubble point is equal to or below the line defined bythe equation log (Gurley)=5.13×10⁻³ (Bubble Point)−1.58.
 26. The articleof claim 21, wherein the Gurley versus bubble point is equal to or belowthe line defined by the equation log (Gurley)=5.13×10⁻³ (BubblePoint)−2.02.
 27. An article comprising a porous PTFE membrane formed bya method comprising forming an extruded lubricated tape of PTFE polymerby a paste extrusion process; stretching the extruded lubricated tapetransversely, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape; then transversely expandingthe tape at an expansion ratio of 20:1 or greater, said porous PTFEmembrane having a water entry pressure versus Gurley number equal to orabove the line defined by the equation WEP=3(Gurley)+2500.
 28. Thearticle of claim 27, wherein said extruded lubricated tape is stretchedtransversely at a ratio of at least 3:1.
 29. The article of claim 27,wherein the water entry pressure versus Gurley is equal to or above theline defined by the equation WEP=3(Gurley)+2900.
 30. The article ofclaim 27, wherein the water entry pressure versus Gurley is equal to orabove the line defined by the equation WEP=3(Gurley)+3100.
 31. Thearticle of claim 27, wherein the Gurley versus bubble point is equal toor below the line defined by the equation log (Gurley)=5.13×10⁻³ (BubblePoint)−1.26.
 32. The article of claim 27, wherein the Gurley number isbetween 1 and 50 seconds.
 33. The article of claim 27, wherein theGurley number is between 5 and 50 seconds.
 34. An article comprising aporous PTFE membrane formed by a method comprising forming an extrudedlubricated tape of PTFE polymer by a paste extrusion process; stretchingthe extruded lubricated tape transversely, and drying the stretched tapeto remove lubricant; longitudinally expanding the resulting tape; thentransversely expanding the tape at an expansion ratio of 20:1 orgreater, said porous PTFE membrane having a water flux rate versusbubble point equal to or above the line defined by the equation log(Water Flux Rate)=−3.5×10⁻³ (Bubble Point)+1.3.
 35. The article of claim34, wherein extruded PTFE extruded lubricated tape is stretchedtransversely at a ratio of at least 3:1.
 36. The article of claim 34,having a water flux rate versus bubble point equal to or above the linedefined by the equation log (Water Flux Rate)=−3.5×10⁻³ (BubblePoint)+1.6.
 37. The article of claim 34, having a water flux rate versusbubble point equal to or above the line defined by the equation log(Water Flux Rate)=−3.5×10⁻³ (Bubble Point)+2.0.
 38. An articlecomprising a porous PTFE membrane formed by a method comprising formingan extruded lubricated tape of PTFE polymer by a paste extrusionprocess; stretching the extruded lubricated tape transversely, anddrying the stretched tape to remove lubricant; longitudinally expandingthe resulting tape; then transversely expanding the tape at an expansionratio of 20:1 or greater, said porous PTFE membrane having a water fluxrate versus mean flow pore size equal to or above the line defined bythe equation log (water flux rate)=16.9 (mean flow pore size)−1.85. 39.The article of claim 38, wherein extruded lubricated tape is stretchedtransversely at a ratio of at least 3:1.
 40. The article of claim 38,having a water flux rate versus mean flow pore size equal to or abovethe line defined by the equation log (Water Flux Rate)=16.9 (mean flowpore size)−1.6.
 41. The article of claim 38, having a water flux rateversus mean flow pore size equal to or above the line defined by theequation log (Water Flux Rate)=16.9 (mean flow pore size)−1.05.
 42. Anarticle comprising a composite of at least one porous PTFE membrane andat least one additional layer, said porous PTFE membrane formed by amethod comprising forming an extruded lubricated tape of PTFE polymer bya paste extrusion process; stretching the extruded lubricated tapetransversely, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape; then transversely expandingthe tape at an expansion ratio of 20:1 or greater, said composite havinga water flux rate versus bubble point equal to or above the line definedby the equation log (Water Flux Rate)=−3.5×10⁻³ (Bubble Point)+1.3. 43.The article of claim 42, wherein said extruded lubricated tape isstretched transversely at a ratio of at least 3:1.
 44. The article ofclaim 42, having a water flux rate versus bubble point equal to or abovethe line defined by the equation log (Water Flux Rate)=−3.5×10⁻³ (BubblePoint)+1.6.
 45. The article of claim 42, having a water flux rate versusbubble point equal to or above the line defined by the equation log(Water Flux Rate)=−3.5×10⁻³ (Bubble Point)+2.0.
 46. The article of claim42, wherein said at least 1 additional layer is selected from the groupconsisting of non-woven, scrim and fabric.
 47. The article of claim 42,wherein said at least one additional layer comprises at least oneadditional layer on each side of the at least one membrane.
 48. Thearticle of claim 42, wherein said at least 1 additional layer comprisesat least one porous membrane.
 49. The article of claim 48, wherein saidat least one porous membrane comprises ePTFE.
 50. The article of claim47, wherein said at least one additional layer on each side comprisesePTFE.
 51. The article of claim 42 in the form of a filter.
 52. Thearticle of claim 42 in the form of a vent.
 53. The article of claim 51in the form of a filter cartridge.
 54. An article comprising a compositeof at least one porous PTFE membrane and at least one additional layer,said porous PTFE membrane formed by a method comprising forming anextruded lubricated tape of PTFE polymer by a paste extrusion process;stretching the extruded lubricated tape transversely, and drying thestretched tape to remove lubricant; longitudinally expanding theresulting tape; then transversely expanding the tape at an expansionratio of 20:1 or greater, said composite further being instantlywettable with water, said composite having a water flux rate versusbubble point equal to or greater than the line defined by the equationlog (Water Flux Rate)=−0.01 (Bubble Point)+1.3.
 55. The article of claim54, wherein said extruded lubricated tape is stretched transversely at aratio of at least 3:1.
 56. The article of claim 54, having a water fluxrate versus bubble point equal to or greater than the line defined bythe equation log (Water Flux Rate)=−0.01 (Bubble Point)+2.48.
 57. Thearticle of claim 54, having a water flux rate versus bubble point equalto or greater than the line defined by the equation log (Water FluxRate)=−0.01 (Bubble Point)+5.0.
 58. The article of claim 54, whereinsaid at least 1 additional layer is selected from the group consistingof non-woven, scrim and fabric.
 59. The article of claim 54, whereinsaid at least one additional layer comprises at least one additionallayer on each side of the at least one membrane.
 60. The article ofclaim 54, wherein said at least 1 additional layer comprises at leastone porous membrane.
 61. The article of claim 60, wherein said at leastone porous membrane comprises ePTFE.
 62. The article of claim 59,wherein said at least one additional layer on each side comprises ePTFE.63. The article of claim 54 in the form of a filter.
 64. The article ofclaim 54 in the form of a vent.
 65. The article of claim 63 in the formof a filter cartridge.
 66. An article comprising a porous PTFE membraneformed by a method comprising forming an extruded lubricated tape ofPTFE polymer by a paste extrusion process; stretching the extrudedlubricated tape transversely, and drying the stretched tape to removelubricant; longitudinally expanding the resulting tape; thentransversely expanding the tape at an expansion ratio of 20:1 orgreater, said porous PTFE membrane being instantly wettable with water,said membrane having a water flux rate versus bubble point equal to orabove the line defined by the equation log (Water Flux Rate)=−0.01(Bubble Point)+1.3.
 67. The article of claim 66, wherein said extrudedlubricated tape is stretched transversely at a ratio of at least 3:1.68. The article of claim 66, having a water flux rate versus bubblepoint equal to or below the line defined by the equation log (Water FluxRate)=−0.01 (Bubble Point)+2.48.
 69. The article of claim 66, having awater flux rate versus bubble point equal to or below the line definedby the equation log (Water Flux Rate)=−0.01 (Bubble Point)+5.0.
 70. Anarticle comprising at least one porous PTFE membrane formed by a methodcomprising forming an extruded lubricated tape of PTFE polymer by apaste extrusion process; stretching the extruded lubricated tapetransversely, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape; then transversely expandingthe tape at an expansion ratio of 20:1 or greater, said porous PTFEmembrane having an oleophobic treatment thereon and an oil rating of atleast 2, said article having a water entry pressure above 1250 kPa and aGurley number of greater than 0 and less than 200 seconds.
 71. Thearticle of claim 70, wherein said article has an oil rating of at least3.
 72. The article of claim 70, wherein said article has an oil ratingof at least
 5. 73. The article of claim 70, wherein said article has awater entry pressure above 2000 kPa and a Gurley number of greater than0 and less than 100 seconds.
 74. The article of claim 70, whereinextruded lubricated tape is stretched transversely at a ratio of atleast 3:1.
 75. An article comprising a porous PTFE membrane formed by amethod comprising forming an extruded lubricated tape of PTFE polymer bya paste extrusion process; stretching the extruded lubricated tapetransversely, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape; then transversely expandingthe tape at an expansion ratio of 20:1 or greater, said porous PTFEmembrane having a Gurley versus bubble point equal to or below the linedefined by the equation log (Gurley)=5.13×10⁻³ (Bubble Point)−1.22 and alight transmission of at least 50%.
 76. The article of claim 75, whereinextruded lubricated tape is stretched transversely at a ratio of atleast 3:1.
 77. The article of claim 75, wherein the Gurley versus bubblepoint is equal to or below the line defined by the equation log(Gurley)=5.13×10⁻³ (Bubble Point)−1.58.
 78. The article of claim 75,wherein the Gurley versus bubble point is equal to or below the linedefined by the equation log (Gurley)=5.13×10⁻³ (Bubble Point)−2.02. 79.A method of filtering a fluid comprising: providing a filter comprisinga porous PTFE membrane formed by a method comprising forming an extrudedlubricated tape of PTFE polymer by a paste extrusion process; stretchingthe extruded lubricated tape transversely, and drying the stretched tapeto remove lubricant; longitudinally expanding the resulting tape; thentransversely expanding the tape at an expansion ratio of 20:1 orgreater, said porous PTFE membrane having a water flux rate versusbubble point equal to or above the line defined by the equation log(Water Flux Rate)=−3.5×10⁻³ (Bubble Point)+1.3; and flowing a fluidcontaining particle through said filter; thereby filtering saidparticles from said fluid.
 80. A method of filtering a fluid comprising:providing a filter comprising a porous PTFE membrane formed by a methodcomprising forming an extruded lubricated tape of PTFE polymer by apaste extrusion process; stretching the extruded lubricated tapetransversely, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape; then transversely expandingthe tape at an expansion ratio of 20:1 or greater, said porous PTFEmembrane having a water flux rate versus mean flow pore size equal to orabove the line defined by the equation log (water flux rate)=16.9 (meanflow pore size)−1.85; and flowing a fluid containing contaminantsthrough said filter; thereby filtering said particles from said fluid.81. A method of filtering a fluid comprising: providing a filtercomprising a composite of at least one porous PTFE membrane and at leastone additional layer, said porous PTFE membrane formed by a methodcomprising forming an extruded lubricated tape of PTFE polymer by apaste extrusion process; stretching the extruded lubricated tapetransversely, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape; then transversely expandingthe tape at an expansion ratio of 20:1 or greater, said composite havinga water flux rate versus bubble point equal to or above the line definedby the equation log (Water Flux Rate)=−3.5×10⁻³ (Bubble Point)+1.3; andflowing a fluid containing particle through said filter; therebyfiltering said particles from said fluid.
 82. A method of filtering afluid comprising: providing a filter comprising a porous PTFE membraneformed by a method comprising forming an extruded lubricated tape ofPTFE polymer by a paste extrusion process; stretching the extrudedlubricated tape transversely, and drying the stretched tape to removelubricant; longitudinally expanding the resulting tape; thentransversely expanding the tape at an expansion ratio of 20:1 orgreater, said porous PTFE membrane instantly wettable with water, saidmembrane having a water flux rate versus bubble point equal to or abovethe line defined by the equation log (Water Flux Rate)=−0.01 (BubblePoint)+1.3; and flowing a fluid containing particle through said filter;thereby filtering said particles from said fluid.
 83. The method ofclaim 81, wherein said filter comprises a hydrophilic composite.
 84. Anarticle comprising a porous PTFE membrane formed by a method comprising:forming an extruded lubricated tape of PTFE polymer by a paste formingprocess; stretching the extruded lubricated tape transversely at a ratioof at least 3:1, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape at a temperature above 327°C.; then transversely expanding the tape at a temperature above 327° C.,said porous PTFE membrane having a Gurley versus bubble point equal toor below the line defined by the equation log (Gurley)=5.13×10⁻³ (BubblePoint)−1.26 and a surface area of at least 20 m²/g.
 85. An articlecomprising a porous PTFE membrane formed by a method comprising formingan extruded lubricated tape of PTFE polymer by a paste forming process;stretching the extruded lubricated tape transversely at a ratio of atleast 3:1, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape at a temperature above 327°C.; then transversely expanding the tape at a temperature above 327° C.,said porous PTFE membrane having a light transmission of at least 50%and a porosity of at least 50%.
 86. An article comprising a porous PTFEmembrane formed by a method comprising forming an extruded lubricatedtape of PTFE polymer by a paste forming process; stretching the extrudedlubricated tape transversely at a ratio of at least 3:1, and drying thestretched tape to remove lubricant; longitudinally expanding theresulting tape at a temperature above 327° C.; then transverselyexpanding the tape at a temperature above 327° C., said porous PTFEmembrane having a bubble point of at least 448 kPa and a Gurley versusbubble point equal to or below the line defined by the equation log(Gurley)=2.60×10⁻³ (Bubble Point)−0.54.
 87. A porous PTFE membraneformed by a method comprising forming an extruded lubricated tape ofPTFE polymer by a paste forming process; stretching the extrudedlubricated tape transversely at a ratio of at least 3:1, and drying thestretched tape to remove lubricant; longitudinally expanding theresulting tape at a temperature above 327° C.; then transverselyexpanding the tape at a temperature above 327° C., said porous PTFEmembrane having a product of matrix tensile strengths in two orthogonaldirections of at least 1.3×10⁵ MPa².
 88. An article comprising a porousPTFE membrane formed by a method comprising forming an extrudedlubricated tape of PTFE polymer by a paste forming process; stretchingthe extruded lubricated tape transversely at a ratio of at least 3:1,and drying the stretched tape to remove lubricant; longitudinallyexpanding the resulting tape at a temperature above 327° C.; thentransversely expanding the tape at a temperature above 327° C., saidporous PTFE membrane having a Gurley versus bubble point equal to orbelow the line defined by the equation log (Gurley)=5.13×10⁻³ (BubblePoint)−1.26 and a product of matrix tensile strengths in two orthogonaldirections of at least 1.3×10⁵ MPa².
 89. An article comprising a porousPTFE membrane formed by a method comprising forming an extrudedlubricated tape of PTFE polymer by a paste forming process; stretchingthe extruded lubricated tape transversely at a ratio of at least 3:1,and drying the stretched tape to remove lubricant; longitudinallyexpanding the resulting tape at a temperature above 327° C.; thentransversely expanding the tape at a temperature above 327° C., saidporous PTFE membrane having a water entry pressure versus Gurley numberequal to or above the line defined by the equation WEP=3(Gurley)+2500.90. An article comprising a porous PTFE membrane formed by a methodcomprising forming an extruded lubricated tape of PTFE polymer by apaste forming process; stretching the extruded lubricated tapetransversely at a ratio of at least 3:1, and drying the stretched tapeto remove lubricant; longitudinally expanding the resulting tape at atemperature above 327° C.; then transversely expanding the tape at atemperature above 327° C., said porous PTFE membrane having a water fluxrate versus bubble point equal to or above the line defined by theequation log (Water Flux Rate)=−3.5×10⁻³ (Bubble Point)+1.3.
 91. Anarticle comprising a porous PTFE membrane formed by a method comprisingforming an extruded lubricated tape of PTFE polymer by a paste formingprocess; stretching the extruded lubricated tape transversely at a ratioof at least 3:1, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape at a temperature above 327°C.; then transversely expanding the tape at a temperature above 327° C.,said porous PTFE membrane having a water flux rate versus mean flow poresize equal to or above the line defined by the equation log (water fluxrate)=16.9 (mean flow pore size)−1.85.
 92. An article comprising acomposite of at least one porous PTFE membrane and at least oneadditional layer, said porous PTFE membrane formed by a methodcomprising forming an extruded lubricated tape of PTFE polymer by apaste forming process; stretching the extruded lubricated tapetransversely at a ratio of at least 3:1, and drying the stretched tapeto remove lubricant; longitudinally expanding the resulting tape at atemperature above 327° C.; then transversely expanding the tape at atemperature above 327° C., said composite having a water flux rateversus bubble point equal to or above the line defined by the equationlog (Water Flux Rate)=−3.5×10⁻³ (Bubble Point)+1.3.
 93. An articlecomprising a composite of at least one porous PTFE membrane and at leastone additional layer, said porous PTFE membrane formed by a methodcomprising forming an extruded lubricated tape of PTFE polymer by apaste forming process; stretching the extruded lubricated tapetransversely at a ratio of at least 3:1, and drying the stretched tapeto remove lubricant; longitudinally expanding the resulting tape at atemperature above 327° C.; then transversely expanding the tape at atemperature above 327° C., said composite further being instantlywettable with water, said composite having a water flux rate versusbubble point equal to or greater than the line defined by the equationlog (Water Flux Rate)=−0.01 (Bubble Point)+1.3.
 94. An articlecomprising a porous PTFE membrane formed by a method comprising formingan extruded lubricated tape of PTFE polymer by a paste forming process;stretching the extruded lubricated tape transversely at a ratio of atleast 3:1, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape at a temperature above 327°C.; then transversely expanding the tape at a temperature above 327° C.,said porous PTFE membrane being instantly wettable with water, saidmembrane having a water flux rate versus bubble point equal to or abovethe line defined by the equation log (Water Flux Rate)=−0.01 (BubblePoint)+1.3.
 95. An article comprising at least one porous PTFE membraneformed by a method comprising forming an extruded lubricated tape ofPTFE polymer by a paste forming process; stretching the extrudedlubricated tape transversely at a ratio of at least 3:1, and drying thestretched tape to remove lubricant; longitudinally expanding theresulting tape at a temperature above 327° C.; then transverselyexpanding the tape at a temperature above 327° C., said porous PTFEmembrane having an oleophobic treatment thereon and an oil rating of atleast 2, said article having a water entry pressure above 1250 kPa and aGurley number of greater than 0 and less than 200 seconds.
 96. Anarticle comprising a porous PTFE membrane formed by a method comprisingforming an extruded lubricated tape of PTFE polymer by a paste formingprocess; stretching the extruded lubricated tape transversely at a ratioof at least 3:1, and drying the stretched tape to remove lubricant;longitudinally expanding the resulting tape at a temperature above 327°C.; then transversely expanding the tape at a temperature above 327° C.,said porous PTFE membrane having a Gurley versus bubble point equal toor below the line defined by the equation log (Gurley)=5.13×10⁻³ (BubblePoint)−1.22 and a light transmission of at least 50%.